Dispersible anthraquinone dyestuffs

ABSTRACT

Difficulty water-soluble anthraquinone dyestuffs free from water-solubilizing groups which dissociate acid in water bearing in at least one Beta -position, either directly or by way of a bridging member, the grouping -Y-O-COOR, wherein Y represents an alkylene group, optionally substituted by a hydroxyl group and R represents an optionally substituted aliphatic, cycloaliphatic or aromatic radical; these dyestuffs being suited particularly for the dyeing of synthetic organic fibers, especially polyethylene glycol terephthalate fibers, affording dyeings on these fibers which have good fastness properties and especially good fastness to light and sublimation.

United States Patent Kolliker et al.

[ Sept. 5, 1972 [54] DISPERSI BLE ANTHRAQUINONE DYESTUFFS [72] Inventors: Hans-Peter Kolliker, Munchstein/ BL; Alfred Staub, Binningen/BL; Peter Hindermann, Flurweg, Bottmingen/BL, all of Switzerland [73] Assignee: Ciba-Geigy AG (Basle, Switzerland 22 Filed: April 1,1970

21 Appl. N01: 24,810

52 U.S Cl. ..260/376, 8/40, 8/39,

260/375, 260/377 [51] Int. Cl. ..C09b 1/50 [5 8] Field of Search ..260/376 [56] References Cited FOREIGN PATENTS OR APPLICATIONS 4,424,909 10/1969 Japan ..260/376 Primary Examiner-Lorraine A. Weinberger Assistant ExaminerE. Jane Skelly Attorney-Wenderoth, Lind & Ponack ABSTRACT being suited particularly for the dyeing of synthetic organic fibers, especially polyethylene glycol terephthalate fibers, affording dyeings on these fibers which have good fastness properties and especially good fastness to light and sublimation.

3 Claims, No Drawings DISPERSIBLE ANTHRAQUINONE DYESTUFFS The present invention relates to sparingly water-soluble anthraquinone dyestufis, usable as dispersion dyestuffs, to processes for their production to the use of 5 these anthraquinone dyestuffs for the dyeing or printing of synthetic organic textile fibers, especially textile fibers made from linear polyesters of aromatic polycarboxylic' acid with polyfunctional alcohols, or made form cellulose esters and, the textile fibers dyed or printed with said dyestuffs.

It has been found that difficulty water-soluble anthraquinone dyestuffs being fee from water-solubilizing groups dissociating acid in water and corresponding to the Formula I,

. A-Y-O- COOR (I) are characterized ,by particularly advantageous properties e.g. good affinity on polyester fibers combined with good fastness to light and sublimation of the dyeings produced therewith.

In the above Formula I A represents the radical of an anthraquinone dyestuff which is linked with Y, in at least one ,8- position, either directly or by way of a bridging member, Y represents an alkylene group, optionally sub stituted by a hydroxyl group, and R represents an optionally substituted aliphatic,

cycloali-phatic or aromatic radical. The anthraquinone dyestufis of Fonnula I are obtained by condensing an anthraquinone compound of the formula II,

A Y OH wherein A and Y have the meaning given under Formula I, with a halogeno formic acid ester of the Formula III,

Hal-COOR m wherein Hal represents chlorine or bromine and R has the meaning given under Formula I.

The starting materials are so chosen that the obtained anthraquinone dyestuff contain no water-solubilizing groups dissociating acid in water, i.e. it contains, e.g. no sulphonic acid groups, carboxylic acid groups or phosphoric acid groups.

The anthraquinone compounds, usable as starting materials and containing, in at least one B-position, a hydroxyalkyl radical bound either directly or by way of a bridging member to the anthraquinone nucleus, can belong to the series of the actual anthraquinonyl compounds as well as to that of the higher condensed derivatives, e.g. to the group of the anthraquinonyl or anthrapyrimidinyl compounds.

The anthraquinone nucleus can contain, in addition .to the substituents Y-O-COOR in B-position, further substituents, e.g. primary amino groups or secondary amino groups which can be substituted by a lower alkyl group such as the methyl, isopropyl or sek. butyl group, a cycloalkyl group such as the cyclohexyl group, a monoor polynuclear aryl group, e.g. phenyl, chlorophenyl, methylphenyl such as the toluylor 2,4,6- trimethylphenyl group, methoxyphenyl, phenoxyphenyl or phenylazophenyl group as well as hydroxy, cyano or nitro groups, or halogens such as fluorine, chlorine or bromine.

A represents in particulara B-anthraquinonyl radical of the formula o i A I wherein V represents hydroxyl or 'NI-I V represents hydrogen, a hydroxyl, unsubstituted amino, lower alkylamino, cyclohexylamino, phenoxyphenylarnino phenylazophenylarnino group or a phenylamino group, the benzene nucleus of which maybe substituted by chlorine, a lower alkyl or lower alkoxy group.

The anthraquinone radical A can be bound direct to Y or by way of a bivalent or trivalent bridging member. Bivalent bridging members can be double-bonding atoms such as oxygen or sulphur, or double-bonding groups. Suitable double-bonding groups are, e.g. those containing heteroatoms, e.g. a COO, CONI-I, O-alkylene0, 'Salkylene 0, Oalkylene--O-phenylene, O-phenylene, O- phenylene0, O-alkylene0-phenylene-O-, -S-phenyleneO-, NH-phenylene, NH- phenylene0 or COOalkylenene--O, the z s0z a O-phenyleneSO- NI-l or -S-phenylene-SO NH- group (whereby R denotes hydrogen or a lower alkyl radical, the alkylene group has at most four carbon atoms and the phenylene group may be substituted by halogen such as chlorine, or lower alkyl groups). Suitable as trivalent bridging member is, in particular, the odicarboxylic acid amide group.

The alkylene group Y contains preferably at most four carbon atoms and can be straight-chained or branched; in the former case it is preferably the 1,2- ethylene or 1,3-propylene group, in the latter case it is the 2-methyl-l,3-propylene or 2,2-dimethyl-l,3- propylene group. If the alkylene group Y is substituted by a hydroxyl group, it represents especially a 2- hydroxy-l ,3-propylene group.

If R represents an aliphatic radical, then it is, e.g. a str ight or branched-chained, optionally substituted alkyl or alkenyl group (in the latter case especially a AZ-alkenyl group) having preferably up to five carbon atoms. As substituents, these aliphatic radicals,especially the alkyl group, can contain, e.g. halogens such as chlorine or bromine, or a lower alkoxy group as well as a carbocyclic ring having, in particular aromatic character such as the phenyl radical, or heterocyclic rings such as the thienyl-(2-, furyl-(2)- or tetrahydrofuryl-(2)-radical.

Cycloaliphatic radicals denoted by R are, e.g. cycloalkyl groups having preferably fiveor six-membered rings and especially the cyclohexyl or methylcyclohexyl group.

When R represents an aromatic radical, then this radical preferably belongs to the benzene, series; it can containjusual non-ionogenic ring substituents. Such substituents are, e.g. halogens such as fluorine, chlorine or bromine, or lower alkyl groups, preferably chlorine or methyl groups.

R represents in particular or lower alkyl group, which may be substituted by chlorine or bromine, a lower alkenyl group, a cyclohexyl group or a phenyl group which may be substituted by one or two substituents selected from chlorine and lower alkyl groups.

Starting materials of the Formula II are for the most part known or they can be produced by methods known per se.

Anthraquinone compounds of the Formula II, in which the radical A is bound to Y by way of oxygen, sulphur, an Oalkylene,

Oalkylene-cycloalkylene-alkylene-Ogroup, can be obtained, e.g. using the process of the German Pat. No. 1,209,680 or of the British Pat. No. 974,404, e.g. by reacting an anthraquinone compound of the Formula IV,

AW (IV) wherein A represents a B-anthraquinonyl radical and W represents halogen, the sulphonic acid group or a phenoxy group, with a compound of the Formula V,

wherein Y has the meaning given under Formula I and X represents oxygen or sulphur and Q represents the direct bond or a bivalent hydrocarbon radical optionally interrupted by oxygen.

Examples of anthraquinone compounds of the Formula IV are: 1-arnino-Z-bromoanthraquinone, 1,4- diaminoQ-bromoanthraquinone, l-amino-4-hydroxy-2 -bromoanthraquinoneor -2-chloroanthraquinone, -1- amino- 4-hydroxy-2-phenoxy-anthraquinone, l-amino- 4-hydroxyanthraquinone-2-su1phonic acid, l-amino-4- phenylaminoanthraquinone-2-sulphonic acid, l-amino- 4-cyclohexylaminoanthraquinone-2-sulphonic acid, 1- amino-4-hydroxy-Z-P-methoxyphenoxy-anthraquinone. Examples of compounds of the Formula V are: glycols such as ethylene-glycol, 1,3-propyleneglycol, 2,2-diethylpropanediol-( 1,3 cyclohexanedimethanol, cyclohexanediethanol cyclohexandei-n-butanol, 2,5- bis-(hydroxymethyl)-tetrahydrofluran, 2,5-bis-(B- hydroxyethyl)-tetrahydrofuran, di-(B-hydroxyethoxy)- benzene, also mor p-(flhydroxyethoxy)-phenol, [Hphydroxy-phenylethyl alcohol, m-hydroxybenzyl alcohol, mercaptoalkyl alcohols such as 2mercaptoethanol, S-mercapto-l-propanol or 4-mercapto-1-butanol.

Starting materials of the Formula II, in which Y is bound to A by way of a SO NH or CONH-group or by way of -Ophenylene-SO NI-I-, Ophenylene-CONH, S-phenylene--SO NH or S- phenylene-CONH-group, can be obtained by reacting a halide of the Formula VI,

A'Q'X Hal .(Vl)

wherein Y A represents a B-anthraquinonyl radical, Q represents the direct bond or a phenylene group which is linked to A by way of oxygen or sulphur, X represents the -CO- or -SO -bond and Hal represents chlorine or bromine,

with an amine of the Formula VII,

NH 'Y-OH wherein Y has the meaning given under Formula I.

Halide's of the Formula VI are, e.g. laminoanthraquinone-2-carbonyl chloride, l-amino-4- phenyaminoanthraquinone 2-carbonyl chloride, 1- amino-4-hydroxy-anthraquinone- 2-phenoxy-3'-carbonyl chloride, l-amino-4-hydroxy-anthraquinone-2 phenoxy-4'-sulfonylchloride, or l -amino-4-hydroxyanthraquinone-2-phenyl-thio-4'-sulfonyl chloride, and amines of the Formula VII are, e.g. ethanolamine or 1 ,3-propanolamine.

The production of the anthraquinone compounds of the Formula H, wherein A represents a methyl group, which is bound to the anthraquinone nucleus A direct or by way of a phenoxy group, is described, e.g. in the French Pat. No. 1,530,985.

Examples of such starting materials of the Formula II are: l,4-diamino-2hydroxymethyl-anthraquinone, 1,4- dihy'droxy-2-hydroxymethyl-anthraquinone, l-amino- 2 -hydroxymethyl-4-phenyl amino-anthraquinone and 1 -hydroxy-2-hydroxymethyl-4-phenylaminoanthraquinone.

The halogeno formic acid esters of the Formula Ill, usable as starting materials, are likewise for the most part known.

Such esters are: e.g. formic acid-alkyl, -alkenyl, cycloalkyl or -aryl esters, e.g., chloroformic acid methyl ester, chloroformic acid ethyl ester, chloroformic acid i'sopropyl ester, chloroformic acid amyl ester, chloroformic acid allyl ester, chloroformic acid cyclohexyl ester, chloroformic acid-'y-chloropropyl ester, chloroformic acid phenyl ester or chloroformic acid-2,4-dimethylphenyl ester, chloroformic acid-4- chlorophenyl ester, as well as the corresponding bromine derivatives.

The reaction of the anthraquinone compounds of the Formula II with the halogeno formic acid esters of Formula HI is preferably performed at low temperatures (0-50 C.) in the presence of acid-binding agents and, optionally, in inert organic solvents.

Suitable acid-binding agents are, in particular, tertiary nitrogen bases such as pyridine, picoline, quinoline, lepidine, aliphatic amines such as trimethylamine and triethylamine, anilines such as N-N-dimethylaniline and N,N-diethylaniline, also alkali metal or alkaline- (Vll) earth metal carbonate, hydrogen carbonates or hydrox- I wherein 6 Preferred anthraquinone dyestuffs of the Formula I, I A" Hal I (XI) which are characterized by a good affinity, by o d A representsaB-anthraquinonyl radical which conlevelling and buildup properties as well as by good fasttains a y y g p in the adjacent l -p ness to sublimation and light on polyethylene glycol and I tel-ephthalate fib correspond to the Formula VIII 5 Hal represents chlorine or bromine, with an amino compound of Formula XII,

0 Nl-I -aryleneQ"Y-OCOOR I xn A wherein X2Y-OCOOR 10 arylene represents a benzene nucleus, optionally substituted by halogen such' as chlorine, or by lower Y alkyl groups, 1

| Q" represents the direct bond, oxygen, or sulphur v V111 and Y and R have the meaning given under Formula I,

V, represents the hydroxyl or amino group, Sociafing acid in water I represents the hydroiql group 9 phenylamino B-Halogeno-anthraquinone compounds of Formula f the benzene of whlch P be XI, usable according to the invention, are for the most stituted by one halogen, such as chlorine or lower part known Examples of these am;

alkoxy group or one to three lower alkyl groups, bromwanthraquinone, 2

2 represents Oxygen, sulphur, the CONH or bromoanthraquinone and l,4-dihydroxy-2-chloro- SO NH-group, or also an -Oalkylene-O anthraquinone.

' group and Amines of the Formula XII to be reacted with the R" represents a lower alkyl group or a phenyl radilatter compounds of the Formula XI can be produced cal, optionally mono-substituted by halogen, such in a known manner e.g. by reacting a nitro compound as chlorine, or by a lower alkyl group such as a Ofthe Formula methyl group.

3Q NO arylene-Q -YOII (XIII) Further anthraquinone dyestuffs, according to the inwherein uarylenen and Y have the meaning given vemlon wh'ch hkewlse are charactenzed by a good above, with a halogeno formic acid ester of the Formuand levelling Property as'by good fasnless la III given above, whereby the condensation is perto hght of the Polyester dyemgs, Produced therewlth formed as described in the foregoing, and then reducare those of the formulas IX and ing the nitro group to the amino group.

Furthermore, anthraquinone dyestuffs falling under Formula I and corresponding to the Formula 0 V1 A I I OH O-COOR I R-NH 0 OH 40 A Y B 2 (IX) (0=alk) n 1-o-Y-o-0 o 0 R and i RNH o o Y A H NH-R (XIV) Q-(O-YOm-O-C 0 o R Y O NH R wherein R represents hydrogen or a lower alkyl group, alk represents lower alkylene,

H I (X) n represents 1 or 2 and R and Y have the meaning given under Formula I wherein and wherein the benzene ring B may be further V V Y and R" have the meaning given under Formonosubstituted by halogen or lower alkyl groups, mula VIII and may be produced by condensing a disulfonated R represents a lower alkyl group or preferably anthraqumone compound ofFommla X hydroge In this specification, including the claims, the term lower applied to alkyl", alkylene and alkoxy SOAH group or moieties means that such groups or moieties have at most five carbon atoms.

Anthraquinone dyestuffs of Formula I, wherein the Y ROOC-O-Y- grouping is linked to the anthraquin- H 0 NH R one nucleus by way of a --NI-I--phenylene, NH phenylene-O- or -NI-IphenyleneS-group may with a compound of Formula XVI also be produced by condensing a B-halogenoanthraquinone compound of Formula XI,

whereby the starting materials are so chosen that the. final dyestuff contains no water-solubilizing groups dis- (XVI) to a monosulfonated anthraquinone compound of Formula XVII RNH (')H (O-alk)n-1OYO-CO0R and then splitting off the sulphonic acid group of this latter compound with a reducing agent,whereby the starting materials are sochosen that the final dyestuff contains no water-solubilizing groups dissociating acid in water.

A further process for the production of anthraquinone dyestuffs of the Formula XIV comprises, oxidizing an anthraquinone compound of Formula XVIII,

(XVIII) wherein R represents hydrogen or a lower alkyl group, to the corresponding quinonimino compound, for example with manganese dioxide andvthen reacting the latter with a compound of the FormulaXVl given above, whereby the starting materials are so chosen that the final dyestuff contains no water-solubilizing groups dissociating acid in water.

The new anthraquinone dyestuffs of the Formula I are yellow to deeply colored, crystalline, difficulty watersoluble substances. They can be obtained analytically pure by recrystallization from organic solvents, but such purification generally not necessary for their use in dyeing.

They are suitable for the dyeing or printing of synthetic organic fibers, e.g. for the dyeing of textile fibers made from linear, high-molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols such as polyethylene glycol terephthalate or poly-( l ,4-cyclohexandimethylol-terephthalate) as well as for the. dyeing of textile fibers made from cellulose- 2-,2 b-acetate or cellulose triacetate. These dyestuffs can, however, also be used for the dyeing of synthetic polyamide fibers such as polyhexamethylene adipamide, polycaprolactarn or polyarninoundecanoic aid as well as for the dyeing of polyamide in the mass.

Furthermore, they are suitable, depending on the composition, for the dyeing of lacquers, oils and waxes, as well as for the dyeing of cellulose derivatives, particularly cellulose esters such as cellulose acetate, in the mass.

Preferably, the dyeing of the mentioned fiber materials with the difficulty water-soluble anthraquinone dyestuffs, according to the invention, is carried out from aqueous dispersion. It is therefore advantageous (XVII) to finely divide the final materials of the Formula I, usable as dispersion dyestuffs, by grinding them with dispersion agents and possibly with further grinding auxiliaries.

Anionic dispersing agents suitable for the purpose are, e.g. the alkylarylsulphonates, the condensation products of formaldehyde with naphthalene sulphonic acid, the lignin sulphonates; suitable non-ionogenic dispersing agents are, e.g. the fatty alcohol or alkylphenyl-polyglycol ethers with higher alkyl radical.

The dyeing of the polyester fibers with the difiiculty water-soluble dyestuffs, according to the invention, from aqueous dispersions,is carried out by the usual processes for polyester materials. Polyesters of aromatic polycarboxylic acids'with polyvalent alcohols are preferably dyed at temperatures of above 100 C. under pressure. But the dyeing can also be performed at the boiling point of the dye bath in the presence of dye carriers, e.g. phenylphenols, polychlorobenzene compounds or similar auxiliaries, or by using the Thermosol process, i.e. pad-dyeing with a subsequent treatment in the heat, e.g. thermofixing at l -210 C. Cellulose-2 y-acetate fibers'are preferably dyed at temperatures of 8085 C. whereas cellulose triacetate fibers, as well as synthetic polyamide fiber material, are advantageously dyed at the boiling point of the dye bath. The use of dye carriers is not necessary in the dyeing of cellulose-2 rfi-acetate or polyamide fibers. Anthraquinone dyestuffs, according to the invention, can also be used for the printing of the stated materials using normal methods.

The anthraquinone dyestuffs of the Formula I, usable as dispersion dyestuffs, draw on to the previously mentioned synthetic organic fiber material, especially on to polyethylene glycol terephthalate textile fibers, very well and they produce thereon strong yellow, orange, red, violet, blue and green dyeings which have good fastness to light, washing, rubbing, perspiration, sublimation, solvents and decatizing. In this respect, mixtures of anthraquinone dyestuffs according to the invention behave particularly favorably.

Furthermore, anthraquinone dyestuffs, according to the invention,can also very well be used in admixture with other dispersion dyestuffs, which are fast to sublimation, for the dyeing of textile material using the paddyeing/thermofixing process. Particularly worthy of note is the fact that dyestuffs of the Formula I produce, in the dyeing of closely woven polyester fabrics or firmly twisted polyester yarns, even dyeings right through.

Moreover, the dyestuffs of the Formula I possess the valuable property of being able to produce on textured polyester fibers, e.g. Crimplene, very deep and nonstreaky dyeings which also have good fastness properties, particularly fastness to light and sublimation. The new anthraquinone dyestuffs also have good stability in the dye liquor and to boiling.

The following examples illustrate the invention. The temperatures are given in degrees Centigrade.

EXAMPLE I 29.9 g of l-amino-2-B-hydroxyethoxy-4-hydroxyanthraquinone are dissolved at 50 in 300 g of pyridine and to the deep red solution are added dropwise, after rapid cooling of the solution to 010 and while the latter is being vigorously stirred, 3l g of chloroformic acid phenyl ester. The reaction is complete after one hour at this temperature. The reaction product of the formula precipitates, on stirring the solution with 300 g of 15 methanol at 20, in a crystalline form; it is filtered off, washed with methanol and dried.

Fibers made from cellulose diand triacetate, as well as from polyethylene terephthalate, are dyed in the aqueous dispersion of this finely divided dyestuff in I very pure and even red shades. The dyeings have very good fastness to light, sublimation and rubbing. v

If, instead of the 29.9 g of l-amino-Z-B-hydroxyethoxy-4-hydroxyanthraquinone, equivalent amounts of an anthraquinone compound listed in the following Table 1, Column II, are used, and instead of the 31 g of chloroformic acid phenyl ester, equivalent amounts of a halogen formic acid ester given in Column III of the same table, using otherwise the same procedure as described in the example, then dyestuffs are obtained which dye polyethylene glycol terephthalate fibers in the shades listed in Column IV of this table, these shades likewise having fastness to light and to sublimatron.

TABLE 1 Shade on polyethylene glycol terophthalatn Number Anthraquinone compound Halogen formic acid ester fibres 2 0 NH"; Red.

3113 01000- CH3 OCHzCHCHzOH H l g 0 OH 3 (|')H fi (|)H CiCOOCHzCCl: Orange.

/\ -ocmomorr I H OH 0 4 h) lTIHz 01000011201 Red.

A -0 CIIz-C1IzOII II I 0 OH -0cn2cn0n ll 0 on 6 7 R d c1cooc1i2-on=cn2 0 --0 CHz- H CH2OH ll 0 on 7 NIIZ l l(l.

II (Inn (.1 (too mm A OCII([l --C1Iz()ll MW II ClCO oon, Orange -scrn01n0rr TAB LE 1-- 'uminucd tvn-phthulntv Number Anthraquinom compound Uqlogz'vn formic acid vstm' Iihrvri 9 NH: CH R 1 v I C10 0 0 on OCHzCH1OCH1CHzOI-I ll 0 0H A00 cmcuQoH ll 0 OH Same as above C100 0 C4H R d, Q 0 0 01111 Red. 010 00 0 11,, Red.

Red. 14 .do 01000 H 15 do O1COOCHzOIIzBr Red.

0 11111; ClCOOCHzCH; Red. II A-0 cmcmoo CHzCIIgO H II 0 OH 17 l) 1 -IH, clcooom Blue.

A I -s-0mcmon V Q-S-CVI'IQCHQOH ll 0 NH;

18- (I) IIIH; CICOOC3H7 Ruby red.

A -SCH2CH:CH:OH

19 0 NH, Red. H l l C1000- 001mmcmocmcmcmon 20 Same as above; CICOOCz s 21 0 NH, Red. H 0100 0- ocmcmo-cmcmon Y 22 Same as above CICOOCzHn 23. 010000 II R d- 0 NH: 2 a H I 0omcm0cmcmo11 Y Red.

24 Same as above H ClC 0" TABLE 1 untinued Shade on polyethylene glycol terephthalate Number Amhraquinone Compound Halogen formic acid ester fibres 25. O NH, Red.

(OCH:CH:)3OH

Red. 26 Same as above 0100002115 27 IFH: C1000 01H; Red.

@ o CH2CH2)40H H O OH Red. 28 Same as above ClCO O@ 29 I vH, 0100002115 Red.

A O CH2CH2 |3HOH 30 (If IIIH: C100 0 01H; Ruby red A -somcm0crncmorr II I O OH

EXAMPLE 31 EXAMPLE 32 40.6 g of 1,5-dihydroxy-4,8-diamino-2-(4'-B-hydroxy-ethoxy)-phenylanthraquinone are homogeneously mixed by stirring in 400 g of N-N-dimethylaniline and to the mixture are added at 5-l0, 16.3 g of chloroformic acid ethyl ester within half an hour. After a further hour at this temperature, the reaction mixture is diluted with 200 g of ethanol, whereupon the dyestuff of the formula OCHgCH OCOOCgH;

7 g of potassium carbonate and 34.5 g of 1-amino-4- hydroxy-Z-/3,'y-dihydroxypropylmercaptoanthraquinone are homogeneously mixed by stirring in 380 g of chlorobenzene and to the mixture are added, at 0-l0 and in the course of 45 minutes, 24.5 g of chloroformic acid isopropyl ester. Stirring afterwards proceeds for a further 2 hours at the same temperature and to the reaction mixture are finally added g of petroleum ether. The reaction product of the formula precipitates as black-violet powder. it is filtered off, washed with petroleum ether and with water and dried.

The aqueous dispersion of the finely divided dyestuff dyes cellulose diand triacetate fibers as well as, in particular, polyethylene glycol terephthalate fibers, in full, even,b]ueish-red shades. The dyeings have good fastness to light, rubbing and wet processing.

The same dyestuff is obtained by using the above example, instead of the 24.5 g of chloroformic acid isopropyl ester, 33.4 g of bromoformic acid isopropyl ester, using otherwise the same procedure as prescribed above.

If, instead of the 34.5 g of 1-amino-4-hydroxy-2-B,ydi-hydroxypropylmercaptoanthraquinone, equivalent SCHzC H-CH2OC O O CH EXAMPLE 41 To a mixture of 350 g of chlorobenzene and 80 g of triethylamine are added 35.1 g of 1,4-diaminoanthraquinone-2,3-dicarboxylic acid-B-hydroxyethylimide and homogeneously mixed by stirring at 40. The suspension is cooled to 0-l0 and'l9 g of chloroformic acid methyl ester are added dropwise in the course of half an hour. To complete the reaction, stirring is car- 10 ried out for a further hour at this temperature. 200 g of TABLE 2 Slmdu on polyothylono glycol Loruphtlmluto Number Anthraquinone compound Halogen formic acid ester fibres 83 I 0 NH; i I M :655 Blueish red.

I OH OH OH 6100003 O NH Do. 34 H s-cmcmon I ii on 35 O NH: CICOOOH; Do. II

AOs-cmomoH ll 0 OH 36 o NH, clcooomcm Do.

H l -s omomon n O OH 37 (N) 11111: ClCOOC4Hn Do.

/\ S-CH2CH2OH as 0 NH; Do.

II I CIC 0 0- A SOH2CH2OH H OH NH; CICOOC;II5 Do.

40 Same as above i I Do.

methanol are then added, whereupon the corresponding'dyestuff of the formula NHZ NHz

precipitates in a finely divided form from the reaction mixture. The dyestuff is filtered off, washed with methanol and dried.

Fabrics made from polyethylene glycol terephthalate fibers are dyed from the aqueous dispersion of the finely divided dyestuff in very pure, even, turquoise blue shades. The dyeings have good fastness to light and to rubbing.

If, in the above example, instead of 19 g of chloroformic acid methylester, 26.3 g of chloroformic acid n-butylester or 21.7 g of chloroformic acid ethylester are used, then two further dyestuffs are obtained which produce turquoise blue dyeings on polyethylene glycol terephthalate fibers. A very similar dyestuff is also obtained by using instead of the 35.1 g of 1,4- diaminoanthraquinone-2,3-dicarboxylic acid ,B-hydroxyethyl-imide, 36.5 g of 1,4-diamino-anthraquinone- 2,3-dicarboxylic acid-B-hydroxypropylimide, and otherwise acylating as in the above example. A somewhat less greenish blue dyestuff is obtained by replacing, in the above example, the 35.1 g of 1,4- diamino-anthraquinone-2,3-dicarboxylic acid-B- hydroxyethyl-imide by 35 g of l-amino-2-B-hydroxyethyl-3-oxo-4,7-diamino-5,6-phthaloyl-dihydroisoindole, proceeding otherwise according to the above example.

EXAMPLE 42 mula o N112 QCIIzOCOO-n-CJI 200 g of methanol are then added to the reaction mixture. The dyestuff is separated by filtration, washed with methanol and dried.

The finely divided dyestuff evenly dyes fibers made from cellulose diand triacetate, as well as polyethylene glycol terephthalate fibers, in aqueous dispersion, in deep blue shades having good fastness to light and to sublimation.

By using, instead of the 34.4 g of l-amino-2-hydroxymethyl-4-phenylaminoanthraquinone, equivalent amounts of an anthraquinone compound given in the following Table 3, Column H, and instead of the 28 g of chloroformic acid-n-amyl ester, equivalent amounts of a halogen formic acid ester given in Column III of the same table, with otherwise the same procedure as stated in the example, dyestuffs are obtained which dye polyethylene glycol terephthalate fibers in the shades listed in Column IV of this table, these shades likewise having fastness to light and sublimation,

'lA "LE 3 Shade on polyethylene glycol tereph- Numhur Anthrnqulnono compound Ilulogon formic acid ester Hmlutv film's 13.... H (l) lTIlI Red II OH olooo -oin II O OH 44 O NH2 1 /CH3 Reddish blue. -CHOH ClCOOCH l CHzCl NI'I l CH:

(I? IIIH; ClCOOCIIzCHzCHzCl Red.

A CHzOH ll 1 O S 21 I EXAMPLE 55 39 g of l-amino-2-B-hydroxyethylme'rcapto-4- anilinoanthraquinone are roughly dissolved at 2025 in 400 g of pyridine and to this solution are added dropwise, during 15 minutes at 5l0, 16.3 g of chloroformic acid ethyl ester. The acylation is completed after a further half an hour at this temperature. The dyestuff of the formula SCHzCHzOC O OCzI-Is precipitates, upon the addition of 400 g of methanol, in crystalline form; the dyestuff is filtered off, washed with methanol and dried.

The finely divided dyestuff very evenly dyes, in aque- I TABLE 4 Shade on polyethylene glycol tereph- Number Anthraquinone compound Halogen formic acid ester thalate fibres 56 E) IIIH;

A s CHzCHrOI-I V CH3 ClCOOCHzCHCIg Blue.

I A CH 57 O N H:

II A s 01120110111011 CIC 0 O CgH; D0.

II O N H- H 58 IIIH;

A o omomoH CH3 Cl-OOOCgH4Cl Violet.

II 0 NH-CH3 I CH;

59 IOI N H;

CICOQCsHu Violet-blue.

II I O NH O C Ha II I I H s 01120110112011 01c 00- Blue. /CH;

O NHC H 61 O N H;

S C H; C Hz 0 H C1COOC;H DO;

II I O N II C H TABLE -(ontinued Shade on polyethylene glycol tbrcph- Number Anthraqumone compound Halogen formic acid ester tlmlnto fibres 62- (I) IIIH: -C 2 5 Violet-blue.

OCH1CH;OH

H I o NH- 1 TH, 010000113 Blue. A s cmcmon y Y A -Q 64 Same as above. 010000 115 Do. 65 -do clcoociHnm) Do.

66.... O NH: Do.

- A 1 on 010 0 o- Os 01250110111011 ll 0 NH- 67 O NH: Do.

S CHzCHzOI-I II I 0 NH- es 0 NH; ClGOOC H Do.

S CHZCHCHZOH II 0 NH- 69 IfH; c1cooc,H5 Violet-blue.

ll 0 NH- 7o c r m, cmcoo-QHS Do.

/\ o-oH,oH,oH

(EH3 I :3! Example 71 to the deep red solution and the reaction product of the formula 45.4 g of 1-am1no-4-hydroxyanthraqumone-2- phenoxy-4'-sulphonic acid-B-hydroxyethylamide are homogeneously mixed by stirring in 350 ml of pyridine and to the mixture are added dropwise at 0-l0, within 65 half an hour, 33 g of chloroformic acid-B-bromoethyl ester and the mixture is maintained at this temperature for a further 2 hours. 300 ml of ethyl alcohol are added O-QSOzNHCHzCHzOCO OCZHiBl gradually precipitates in a fine-crystalline form. The reaction product is filtered off, washed on the filter with ethyl alcohol and afterwards dried.

The finely divided dyestuff dyes polyethylene glycol terephthalate fibers, in aqueous dispersion, in brilliant red shades having very good fastness to light, sublimation and rubbing.

By using, instead of the 45.4 g of l-amino-4-hydrox hydroxyethyl-amide,

halogen formic acid ester, given in Column III of the.

same table, with otherwise the same procedure as described in the example, dyestuffs are obtained which dye polyethylene glycol terephthalate fibers in the shades listed in Column IV of this table, these shades yanthraquinone2-phenoxy-4'-sulphonic acid-B- 10 likewise having fastness to light and sublimation.

TABLE 5 Shade on polyethylene glycol terephthaluto fibres No. Anthraquinone compound Halogen formic acid ester 72 O 1TH; CICOOCH: Red-violet.

-OSO2NHCH:CH:OH

73 O NHz C1-C O O CzH4B1' DO.

,U l o-{ -SO3NHCHCHOH o-Q-somnomomon 0 NH 74 c 1 111, o1oooczo15 Do.

' O-SO:NHCH2CH1CH2OH II 0 NH2 75 I-|IH1 0100001115 Ruby red.

A S- S0zNHCH1CfH-CH1OH II 0 0E 16 1 1m (210000111, Do.

s@ s OQNHCHPCHQCHEOH 77 JI 1 1m 0100002115 Red.

Q-o-Q s OZNHCHICHrOH 78 0 NH, Do,

II I 010 o 0- s omnorncmorr ll 0 o H 19 IIIH, CICOOCAHQ Do.

@/\ 0 -s omnomomoir II o o H TABLE 5 C ontinued 39.1 g of l-amino-4-hydroxy-2-( 4' B-hydroxyethoxyphenoxy)-anthraquinone are sprinkled into 350 ml of pyridine at 35-40 while the mixture is being vigorously stirred. The mixture is cooled to lO-l 5 and to it are added, in small portions, 43.3 g of chloroformic acid tribromoethyl ester. Stirring is maintained at this temperature until the starting material can no longer be detected by thin-layer chromatography.

With the addition of 350 ml of methanol, the formed dyestuff of the formula 1% w 25 O--OCH2CHzOCOOCH2CBH I I 30 0 0H precipitates in the form of fine dark-red crystals from the reaction mixture. The dyestuff is filtered off, washed with methanol and water and dried.

The finely divided dyestuff dyes polyethylene terephthalate fibers, from aqueous dispersion, in even blueish-red shades having excellent fastness to light, sublimation and rubbing.

If, in the above example, instead of 39.1 g of lamino-4-hydroxy-2-(4-B-hydroxyethoxy-phenoxy)- anthraquinone 40.7 g of l-amino-4-hydroxy-2-(4'-B- hydroxyethoxy-phenylthio-anthraquinone and the same procedure as prescribed above are used, then a little more blueish red dyestuff having the same good dyeing properties is obtained.

EXAMPLE 82 To a solution of 31.2 g of l-aminoanthraquinone-Z- No. Anthraquinone compound Halogen formic acid ester 80 (I) 1TH; ClCOOCzHs Rubyred.

@AOs--s0mncmomon EXAMPLE 81 pyridine are added in small portions at 0-l0, while ll l A CONHCHzCHzCH2OCOO--CH:

is precipitated as fine red powder. The dyestuff is filtered off, washed with water until the reaction is neutral and with a little methanol, and then dried.

From aqueous dispersion, the finely divided dyestuff dyes fibers made from cellulose diand triacetate, as well as, in particular, fibers made from polyethylene terephthalate, in very even red shades having good fastness to light and to rubbing.

By using, instead of the 31.2 g of l-aminoanthraquinone-2-carboxylic acid-B-hydroxypropylamide, equivalent amounts of an anthraquinone compound given in the following Table 6, Column [1, and instead of the 46.6 g of chloroformic acid-p-methoxyphenyl ester, equivalent amounts of a halogen formic acid ester given in Column ill of the same table, with otherwise the same procedure as given in the example, dyestuffs are obtained which dye polyethylene glycol terephthalate fibers in the shades listed in Column IV of this table, these shades likewise having fastness to carboxylic acid-y-hydroxypropylamide in 300 ml of 50 light and to sublimation.

TABLE 6 Shade on polyethylene glycol terephtha- N 0. anthraquinone compound Halogen formic acid ester late fibres 83 O NH Rod.

1 2 CIC 0 ocQNHCHZCHICHZOH l on:

84 0 112 /CH1 Blue.

' 010 o 0 CH CO.\'HCH:CH:OH

TABLE 6 -Conlinued Shade on pfulyellhylenf l g yco tvrcp 1t 1a- Halogen formic acid ester late fibres No. Anthraquinone compound Blueish red.

I Q-cormcmcmon Blue.

C100 0 CH;

'Red.

CICOOCzHs Q 111112 A CONHCH:CH2OH \J Green.

CICOOCzHs COO CHgCH OH Yellovi'ish green.

ClCOOCzH;

Red.

Blueish red.

CICOOC4H9 O NH:

Blue.

CICOO C111 TABLE 6 (ominucd Slnido on polyolhylono glycol tvrophthm No. Anthraquinone compound Halogen formic acid ester Into fibres 94 ll Ha CICOOCJI, Red.

95 ITIH; ClCOO C ll; Blue.

00 0 o ,omcnio oliic mon Y 0 NII 96 (I) IIIH, 01C 0 O C4H0 D0- OC o 0 01110117011 ll 0 NH EXAMPLE 97 EXAMPLE 98 42.3 g of 1-hydroxy-2-B-hydroxyethylsulphonyl-4- I phenylaminoanthraquinone are homogeneously mixed OH gsoiomomo o 0 00411, Y

is precipitated, by the addition of 300 ml of methanol, in a fine-crystalline form from the reaction mixture. The dyestuff is then filtered off, washed on the filter with methanol and dried.

With the finely divided dyestuff are obtained on polyethylene terephthalate fibers, from aqueous disp ersion, even, deep, reddish blue shades having very good fastness to light and to sublimation.

A reddish blue dyestuff possessing similar properties is obtained by using, instead of 34 g of chloroformic butyl ester, 19 g of chloroformic acid methyl ester; a greenish blue dyestuff having similar good fastness properties is obtained by using, instead of the 42.3 g of 1- hydroxy-Z-B-hydroxyethylsulphonyl-4-phenylaminoanthraquinone, 42.2 g of 1-amino-2-B-hydroxyethylsulphonyl-4-phenylaminoanthraquinone, proceeding otherwiseaccording to the above example.

31.9 g of l,4-dihydroxy-2-bromoanthraquinone and 56 g of 4-(B-ethoxycarbonyloxy-ethoxy)-aniline are stirred up in 350 g of boiling ethylene glycol monomethyl ether for 15 hours; to the deep violet-red reaction solution are added, at 100, ml of water and the solution is cooled to room temperature. The precipitated crystalline dyestuff of the formula is then filtered off, washed with methanol and dried.

From an aqueous dispersion, the finely-divided dyestuff dyes fabric, made from polyethylene terephthalate fibers,in even red-violet shades having excellent fastness to light and to sublimation.

By using, instead of the 31.9 g of 1,4-dihydroxy-2- bromoanthraquinone, equivalent amounts of an anthraquinone compound, given in the following Table 7, Column II, and instead of the 56 g of 4'-(B,-ethoxycarbonyloxy-ethoxy)-aniline, equivalent amounts of an aniline derivative given in Column II of the same table, with otherwise the same procedure as described in the example, dyestuffs are obtained which dye polyethylene glycol terephthalate fibers in the shades listed in Column IV of this table, these shades likewise having fastness to light and to sublimation.

TABLE 7 Shade on polyethylene glycol terephthalate fibres Anthfaquinone Number compound Halogen formic ac1d ester Red.

NH OCHzCHaOCOOCH:

Orange.

NE CHaCHzQCOOCzED Red.

CIJH NH O CHzCHCHaCO 0 C111:

Red.

Red.

NH; OCHyCHgO-COOQH.

Red.

NH: (OCHzC-HzhOCOOCzH:

Red.

Red.

NH; CHzCHzCHzOCOOCHa is precipitated from the mixture by the addition of 450 gof methanol. It is-filtered ofi, washed with methanol and dried.

From its finely divided aqueous dispersion, this dyestuff dyes polyethylene terephthalate fibers in intensely yellow shades having fastness to sublimation.

Very deeply colored, pure yellow dyestufis, having very goodfastness to sublimation, are obtained on polyethylene terephthalate fibers by replacing, in the above example, the 30.4 g of 1(N),9-(2'-methyl)- pyridin-2-B-hydroxyethylaminoanthraquinone by 32.3 g of 1(N),9-(N)-pyrimidino-2-B-hydroxyethylthio-4-aminoanthraquinone and acylating by using either the same amount of'chloroformic acid phenyl ester or by using 21.7 g of chloroformic acid ethyl ester, under otherwise the same conditions.

EXAMPLE 108 To a solution of 800 g of 96 percent sulphuric acid and 22 g of o-boric acid are added, at 4050 and within one-half hour, 48 g of l,5-dihydroxy-4,8- diaminoanthraquinone-3,6-disulphonic acid. The solution is cooled to.10 and to it are then added 38 g of monophenoxy-diethyl carbonate. Stirring is maintained for half an hour at and the temperature then a1- lowed to rise within half an hour to room temperature. After this period of time, the reaction mixture is poured on to 2 liters of ice/methanol (30 percent methanol) and then heated for 4 hours at 60.

The product of the formula NH2 O is filtered off, washed with 5 percent brine and dried.

33 g of the dried product are suspended in 400 ml of 50 percent methanol, to the suspension are added 40 ml of concentrated ammonia and to the whole are added dropwise 18 g of sodium hyposulphite in 60 ml water, the mixture being .then heated for one hour to 4050.

oomornooooozm Hots H NH;

these shades being listed in Column IV of the same ta- NH: O OH a Yum OCHzCHgOC 0002B;

EXAMPLE 109 28.6 g of l,5-dihydroxy-4,8-diaminoanthraquinone are added to 270 ml of percent sulphuric acid at 20 30 within 25 minutes. The yellowish brown solution is cooled to 05 and oxidized with 18 g of manganese dioxide, within 30 minutes, to the corresponding quinonimine. The deep-blue solution of the quinonimine is filtered through a glass frit, the residue washed with 180 ml of 96 percent sulphuric acid, cooled to -30 and 30.5 g of B-mono-phenoxydiethyl carbonate are added. The reaction at this temperature is completed after 2 hours. Then reaction product of the formula NH; on

HY NH:

precipitates out in crystalline form as the solution is stirred with ice. The reaction product is filtered off,

OCHZCHQOO OOCzHs washed neutral with water, subsequently treated with.

methanol and dried.

lThis dyestufi is identical to that stated under Examp e 3 1.

If, instead of the 28.6 g of l,5-dihydroxy-4,8- diaminoanthraquinone equivalent amounts of I the anthraquinone compound given in the following Table 8, Column II, are used, or if the 30.5 g of )9- monophenoxydiethyl carbonate are replaced with equivalent amounts of the phenoxy compound given in Column III of the same table, with otherwise the same procedure as described in the Example 109, then dyestuffs are obtained which dye polyethylene glycol terephthalate fibers in shades having similar properties;

The dyestuff of the formula ble.

TABLE 8 Shade on polyethylene yeol terephthalate Number Anthrsquinone compound Halogen formic acid ester fibres NH: 0 0H Blue.

| H l H- OCHzCHzOOOOCHa 5 II I H O NH:

111 Same as above /CH; Do.

HO cmom-o-o 0 0 CH\ 112 -do Do.

H- 0CH CH:OCQOC4Hv-I1 TABLE 8 Continued Shade on polyethylene my): I l torontnnh Number Anthraquinono compound Halogen formic acid ester fihr s 114 ..do CH3 D0.

115 do I OH; D0.

1m do I Do.

HQOCHzCHz-O-4JOOQ 7 CH3 111 do D0.

HQ-O omom-o-oo o H 115.--, do D0.

HO CH CHg-0-COO-Cl I HQO CHaCHr-O-COOQ l CH;

120 NH: 0 OH DO.

| i H O-CHz-CH2-CH:-OCOOC:H5

OH O NH:

121 Same as above Do.

' H- OCH2Cl3HCHzO-COOC2H5 122 ..do Do.

H O-CHz-CH:-OCH:CH:OCOOC2H5 H- OCHaCHzCHnQCHzCHzGHzOCOOC2H5 12A do Do.

H -0CHICHIOCHzCHzCH2O-COOCH5 125 do Do.

a H- OCHQCHBCHKOCHICHIO COOCZH;

126 do Do.

. H OCHCHOCOOCH2CHBT 121 CHaNH 0 OH Do.

A l H -OCH:CH:O--COOC2H5 l I OH O NH-CHa 128 C:HsIl IH/?\ (RH Same as above Do.

I Y OH 0 NHCzHE lEXAli/liLE 129 within a further half hour, oxidized with 18 g of man-- ganese dioxide to quinonimine. The obtained deep blue I solution is clarified through a glass frit and to the solu- 28.6 g of l,5-dihydroxy-4,8-diaminoanthraquinone 65 tion are added, at 10 to -5, 31 g of B-(pare introduced in small portions within half an hour at methylphenoxy)-ethylmethyl carbonate. At this tem- 25 into 270 ml of 96 percent sulphuric acid, whereuperature the reaction is completed after one hour, the pon the yellowish-brown solution is cooled to 0 and, formed reaction product of the formula 

2. An anthraquinone dyestuff as defined in claim 1 and corresponding to the formula wherein R'' represents hydrogen or lower alkyl, n represents 1 or 2, Y'' is lower alkylene, and R'''' is lower alkyl, phenyl or phenyl substituted by one or two substituents selected from chlorine and lower alkyl.
 3. An anthraquinone dyestuff as defined in claim 2 and having the formula 